The synthesis of ethyleneimines from ?-haloaminoethane

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Scotland, Kevin M.
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University of Guelph

This thesis describes a simple method for the synthesis of ethyleneimines. Ethyleneimines have historically found use as cancer drugs as well as starting materials for amines, amides and N-heterocycles. However, there is very little accurate data on some of these compounds most basic characteristics; one such characteristic is the energy of the nitrogen inversion barrier of ethyleneimines. Herein, the inversion barriers were calculated with the CBS-Q method and compared with experimental data obtained from dynamic NMR. The primary aim of this investigation was to develop a large scale method for ethyleneimines on a kilogram scale. To this end we investigated the reaction of primary amines with 1,2-dibromoethanes, in a variety of polar and non polar solvents using different bases. These reactions failed to produce a viable synthetic method. This prompted the development of a high yielding synthesis for the 1-bromo-(2-alkylamino)ethane·hydrobromide, utilizing the amino alcohol, and a 48% hydrobromic acid solution, resulting in yields of ranging from 81-89% for R=Me, Et, 'i'-Pr, ' t'-Bu, Ph.

ethyleneimines, beta-haloaminoethane, synthesis, inversion barriers